Fe-Co-K/ZrO2催化CO2加氢制低碳烯烃

doi:10.15541/jim20210044

无机材料学报 ›› 2021, Vol. 36 ›› Issue (10): 1053-1058.DOI: 10.15541/jim20210044 CSTR: 32189.14.10.15541/jim20210044

所属专题：【虚拟专辑】碳中和(2020~2021)

Fe-Co-K/ZrO₂催化CO₂加氢制低碳烯烃

刘强(), 丁杰(), 纪国敬, 胡绢敏, 顾浩, 钟秦()

南京理工大学化学与化工学院, 南京 210094

收稿日期:2021-01-25 修回日期:2021-03-30 出版日期:2021-10-20 网络出版日期:2021-04-25
通讯作者: 丁杰, 讲师. E-mail: tonlyjding@njust.edu.cn; 钟秦, 教授. E-mail: zq304@njust.edu.cn
作者简介:刘强(1996-), 男, 硕士研究生. E-mail: qiaangliu@163.com
基金资助:
国家自然科学基金(21908108);江苏省科技项目(BK20180449);中央高校基本科研业务费专项资金资助(30920041108);江苏高校品牌专业建设工程资助项目

Fe-Co-K/ZrO₂ Catalytic Performance of CO₂ Hydrogenation to Light Olefins

LIU Qiang(), DING Jie(), JI Guojing, HU Juanmin, GU Hao, ZHONG Qin()

School Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, China

Received:2021-01-25 Revised:2021-03-30 Published:2021-10-20 Online:2021-04-25
Contact: DING Jie, lecturer. E-mail: tonlyjding@njust.edu.cn; ZHONG Qin, professor. E-mail: zq304@njust.edu.cn
About author:LIU Qiang(1996-), male, Master candidate. E-mail: qiaangliu@163.com
Supported by:
National Natural Science Foundation of China(21908108);Scientific and Technological Project of Jiangsu Province(BK20180449);Fundamental Research Funds for the Central Universities(30920041108);Top-notch Academic Programs Project of Jiangsu Higher Education Institutions

摘要/Abstract

摘要：

近年来, 随着化石资源的消耗和CO₂的大量排放, 人类面临的能源危机和温室效应问题日益严峻, 而铁基催化剂催化CO₂加氢直接合成烯烃是实现CO₂减排及CO₂转化与利用的最佳途径之一。本研究采用浸渍法制备了氧化锆(ZrO₂)负载铁钴催化剂(Fe-Co/ZrO₂)和ZrO₂负载铁钴钾催化剂(Fe-Co-K/ZrO₂)用于催化CO₂加氢制低碳烯烃(C₂⁼-C₄⁼), 重点考察了K含量对催化反应活性的影响。活性测试结果表明, 在300 ℃和1.5 MPa下, 加入K使CO₂转化率由40.8%提高到44.8%, 低碳烯烃选择性从0.23%增至68.5%, 并提高了反应性能的稳定性。表征结果显示, 加入K使Fe物种的外层电子密度增大, 提高了Fe对CO₂的吸附强度, 促进了碳化铁的形成, 并有利于CO₂在Fe物种上吸附后发生直接解离, 提升了CO₂加氢制低碳烯烃性能。

关键词: CO₂加氢, 低碳烯烃, 铁钴催化剂, K的影响

Abstract:

In recent years, with the consumption of fossil resources and the large amount of CO₂ emissions, the energy crisis and the greenhouse question become deeply serious. The direct synthesis of olefins by CO₂hydrogenation with iron-based catalysts is one of the best ways to achieve CO₂ reduction. In this study, zirconia (ZrO₂)-supported iron-cobalt catalyst (Fe-Co/ZrO₂) and ZrO₂-supported iron-cobalt-potassium catalyst (Fe-Co-K/ZrO₂) were prepared by impregnation method, which were used for CO₂ hydrogenation to light olefins (C₂⁼-C₄⁼), and the effect of K on the catalytic activity were investigated emphatically. At the condition of 300 ℃ and 1.5 MPa, the activity test show that addition of K increases the CO₂ conversion from 40.8% to 44.8%, improves the selectivity of light olefins from 0.23% to 68.5%, and raises the stability of catalytic performance. The characterization results show that introduction of K improves electron cloud density of the iron species, enhances adsorption strength of the Fe to CO₂, promotes the formation of iron carbide, and facilitates direct dissociation of CO₂ after adsorption on Fe species, thus boosts the performance of CO₂ hydrogenation to light olefins.

Key words: CO₂ hydrogenation, light olefin, iron-cobalt catalyst, effect of K

中图分类号:

TQ426
TK91

刘强, 丁杰, 纪国敬, 胡绢敏, 顾浩, 钟秦. Fe-Co-K/ZrO₂催化CO₂加氢制低碳烯烃[J]. 无机材料学报, 2021, 36(10): 1053-1058.

LIU Qiang, DING Jie, JI Guojing, HU Juanmin, GU Hao, ZHONG Qin. Fe-Co-K/ZrO₂ Catalytic Performance of CO₂ Hydrogenation to Light Olefins[J]. Journal of Inorganic Materials, 2021, 36(10): 1053-1058.

图/表 13

图1 不同温度下x-FCK/ZrO2催化CO2加氢的CO2转化率(a)和低碳烯烃选择性(b); 300 ℃下x-FCK/ZrO2催化产物分布(c)

Fig. 1 CO2 conversion (a) and light olefins selectivity (b) of CO2 hydrogenation by x-FCK/ZrO2 at different temperatures and catalytic production distribution of x-FCK/ZrO2 at 300 ℃(c) Colorful images are available on website

图2 0-FCK/ZrO2和0.3-FCK/ZrO2的催化稳定性测试

Fig. 2 Stability experiments of 0-FCK/ZrO2 and 0.3-FCK/ZrO2

图3 0-FCK/ZrO2(a,b)和0.3-FCK/ZrO2(c,d)的TEM照片

Fig. 3 TEM images of 0-FCK/ZrO2 (a,b) and 0.3-FCK/ ZrO2 (c,d)

图4 催化剂煅烧后(a)和还原后(b)的XRD谱图

Fig. 4 XRD patterns of the calcined (a) and reduced (b) catalysts

图5 不同K含量催化剂的H2-TPR图谱

Fig. 5 H2-TPR spectra of catalysts with different K contents

图6 不同K含量催化剂的CO2-TPD图谱

Fig. 6 CO2-TPD spectra of the catalysts with different K contents

图7 0-FCK/ZrO2和0.3-FCK/ZrO2的XPS-Fe2p谱图

Fig. 7 XPS spectra of Fe2p over 0-FCK/ZrO2 and 0.3-FCK/ZrO2

图8 0-FCK/ZrO2(a)和0.3-FCK/ZrO2(b)的原位红外谱图(仅通入CO2); 0-FCK/ZrO2(c)和0.3-FCK/ZrO2(d)的原位红外谱图(通入CO2和H2)

Fig. 8 In-situ DRIFTS of 0-FCK/ZrO2 (a) and 0.3-FCK/ZrO2 (b) with pure CO2 introduced, and in-situ DRIFTS of 0-FCK/ZrO2 (c) and 0.3-FCK/ZrO2 (d) with CO2 and H2 introduced

图S1 0.3-FCK/ZrO2催化反应产物的质谱

Fig. S1 Mass spectra for the 0.3-FCK/ZrO2 of reactive production

图S2 0-FCK/ZrO2(a~c)和0.3-FCK/ZrO2(d~g)的SEM-EDS 表征

Fig. S2 SEM-EDS analyses of 0-FCK/ZrO2 (a-c) and 0.3-FCK/ZrO2 (d-g)

图S3 0-FCK/ZrO2(a)和0.3-FCK/ZrO2(b)的XPS-Co2p谱图

Fig. S3 XPS spectra of Co2p over 0-FCK/ZrO2 (a) and 0.3-FCK/ZrO2 (b)

图S4 反应85 h后催化剂的XRD谱图

Fig. S4 XRD patterns of the catalysts after reaction for 85 h

图S5 x-FCK/ZrO2的H2-TPD图谱

Fig. S5 H2-TPD spectra for x-FCK/ZrO2

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Fe-Co-K/ZrO₂催化CO₂加氢制低碳烯烃

Fe-Co-K/ZrO₂ Catalytic Performance of CO₂ Hydrogenation to Light Olefins

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